Composition having a muguet odor

ABSTRACT

A composition of matter including:
         a) at least one compound of formula (I)       

     
       
         
         
             
             
         
       
         
         
           
             in the form of any one of its isomers or a mixture thereof; wherein R 1  represents a hydrogen atom or a C 1-2  alkyl group; R 2  represents a hydrogen atom or a methyl group; and R represents a group of formula —[CH 2 ] n C(Me) 2 OH, wherein n is 0, 1 or 2; with R being, relative to position 1, an ortho, meta or para substituent of the aromatic ring; and 
             b) at least one compound of formula 
           
         
       
    
     
       
         
         
             
             
         
       
         
         
           
             in the form of any one of its isomers or a mixture thereof; wherein R 1 , R 2  and R have the same meaning as defined in formula (I);
 
uses of the composition of matter as perfuming ingredients, perfuming compositions and in consumer products, along with a process to prepare the composition of matter.

This application is a 371 filing of International Patent ApplicationPCT/EP2018/051057 filed Jan. 17, 2018, which claims the benefit ofEuropean application no. 17151937.4 filed Jan. 18, 2017.

TECHNICAL FIELD

The present invention relates to the field of perfumery. Moreparticularly, it relates to a composition of matter comprising at leastone compound of formula (I) and at least one compound (II) as perfumingingredients as well as the composition and the consumer productincluding such composition of matter. The process to obtain theinvention's composition of matter is also part of the present invention.

BACKGROUND

One of the key ingredients in the perfumery industry is Lyral®(4/3-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carbaldehyde; originInternational Flavors & Fragrances, USA). However the use of saidingredient, appreciated for this floral, lily of the valley,hydroxycitronellal odor note which is different from the note impartedby Lilial® (2-methyl-3-[4-(2-methyl-2-propanyl)phenyl]propanal,trademark from Givaudan-Roure SA, Vernier, Suisse), has been restrictedas it is listed as an allergen.

So, there is a need to develop novel perfuming ingredients which couldbe used as Lyral® replacers.

The present invention provides a composition of matter comprising atleast one compound of formula (I) and at least one compound of formula(II) having characteristic odors very close to Lyral®.

To the best of our knowledge, only one closely related structuralanalogue of compound of formula (I) and of compound of formula (II) hasbeen reported in the literature as perfuming ingredient. Actually,3-(4-(2-hydroxypropan-2-yl)phenyl)butanal has been reported in U.S. Pat.No. 4,491,537 as having a green, woody, peach like aroma, i.e. a totallydifferent organoleptic profile from the present invention's compounds.

Another analogue,3-(3-(3-hydroxy-3-methylbutyl)phenyl)-2-methylpropanal, has beendisclosed in WO 2014207205 without specifying its organolepticproperties. Said compound has been used as an intermediate towards theperfuming ingredient2-methyl-3-(3-(3-methylbut-3-en-1-yl)phenyl)propanal.

Both prior art documents do not report or suggest any organolepticproperties of the composition of matter comprising compounds of formula(I) and compound of formula (II), or any use of said compounds in thefield of perfumery.

SUMMARY OF THE INVENTION

The invention relates to a composition of matter comprising at least onecompound of formula (I) and at least one compound of formula (II) whichcould be used as a Lyral® replacer.

So, a first object of the present invention is a composition of mattercomprising:

-   -   a) at least one compound of formula

in the form of any one of its isomers or a mixture thereof; wherein R¹represents a hydrogen atom or a C₁₋₂ alkyl group; R² represents ahydrogen atom or a methyl group; and R represents a group of formula—[CH₂]_(n)C(Me)₂OH, wherein n is 1 or 2; said R being, relative toposition 1, an ortho, a meta, a para substituent of the aromatic ring ora mixture thereof; and

-   -   b) at least one compound of formula

in the form of any one of its isomers or a mixture thereof;wherein R¹, R² and R have the same meaning as defined in formula (I);said R being, relative to position 1, an ortho, a meta, a parasubstituent of the aromatic ring or a mixture thereof.

A second object of the present invention is the use as perfumingingredient of a composition of matter, comprising compound of formula(I) and compound of formula (II), as defined above.

A third object of the present invention is a perfuming compositioncomprising

-   i) at least a composition of matter, comprising compound of    formula (I) and compound of formula (II), as defined above;-   ii) at least one ingredient selected from the group consisting of a    perfumery carrier and a perfumery base; and-   iii) optionally at least one perfumery adjuvant.

Another object of the present invention is a perfumed consumer productcomprising at least a composition of matter, comprising compound offormula (I) and compound of formula (II), as defined above or aperfuming composition as defined above.

Another object of the present invention is a process to prepare thecomposition of matter as defined above comprising the step of reactingallyl alcohol or crotyl alcohol with compound of formula

wherein R and R¹ have the same meaning as defined above; said R being,relative to position 1, an ortho, a meta, a para substituent of thearomatic ring or a mixture thereof; under Heck coupling conditions.

A last object of the present invention is a method to confer, enhance,improve or modify the odor properties of a perfuming composition or of aperfumed article, which method comprises adding to said composition orarticle an effective amount of at least a composition of matter asdefined above.

DESCRIPTION OF THE INVENTION

Unless stated otherwise, percentages (%) are meant to designate percentby weight relative to the total weight of the composition.

Surprisingly, it has now been discovered that a composition of matter,comprising at least one compound of formula (I) and at least onecompound of formula (II), exhibits a very interesting odor note with alily of the valley twist in the direction of Lyral® which isparticularly appreciated. This composition of matter has also never beendisclosed.

A first object of the present invention is a composition of mattercomprising

-   -   a) at least one compound of formula

in the form of any one of its isomers or a mixture thereof; wherein R¹represents a hydrogen atom or a C₁₋₂ alkyl group; R² represents ahydrogen atom or a methyl group; and R represents a group of formula—[CH₂]_(n)C(Me)₂OH, wherein n is 1 or 2; said R being, relative toposition 1, an ortho, a meta, a para substituent of the aromatic ring ora mixture thereof; and

-   -   b) at least one compound of formula

in the form of any one of its isomers or a mixture thereof;wherein R¹, R² and R have the same meaning as defined in formula (I);said R being, relative to position 1, an ortho, a meta, a parasubstituent of the aromatic ring or a mixture thereof. Said compositionof matter can be used as perfuming ingredient, for instance to impartodor notes of the lily of the valley type in the direction of Lyral®.

For the sake of clarity, by the expression “R¹, R² and R have the samemeaning as in formula (I)”, or similar, it is meant the normal meaningunderstood by a person skilled in the art, i.e. that the invention'scomposition of matter comprises compounds of formula (I) and (II)wherein R¹ group of compound of formula (I) is identical to R¹ group ofcompound of formula (II), R² group of compound of formula (I) isidentical to R² group of compound of formula (II) and R group ofcompound of formula (I) is identical to R group of compound of formula(II). In other words, the substituents of the compound of formula (I)are identical to the substituents of the compound of formula (II).

For the sake of clarity, by the expression “composition of matter”, orsimilar, it is meant the normal meaning understood by a person skilledin the art, i.e. that at least two different compounds (which are notstereoisomers) are present. According to any one of the aboveembodiments, the invention's composition of matter may comprise at leastone compound of formula (I) in an amount comprised between 0.5% w/w and60% w/w and at least 40% w/w of at least one compound of formula (II),relative to the total weight of the composition of matter. Preferably,the invention's composition of matter may comprise compound of formula(I) in an amount comprised between 0.5% w/w and 49% w/w and at least 50%w/w of compound of formula (II), relative to the total weight of thecomposition of matter. Preferably, the invention's composition of mattermay comprise compound of formula (I) in an amount comprised between 1%w/w and 30% w/w and at least 70% w/w of compound of formula (II),relative to the total weight of the composition of matter. Even, morepreferably, the invention's composition of matter may comprise compoundof formula (I) in an amount comprised between 1% w/w and 15% w/w and atleast 85% w/w of compound of formula (II), relative to the total weightof the composition of matter.

For the sake of clarity, by the expression “any one of” its isomers or amixture thereof, or similar, it is meant the normal meaning understoodby a person skilled in the art, i.e. that the invention's compound canbe a pure enantiomer (if chiral), a mixture of enantiomers (mixture ofstereoisomers), a pure regioisomer, a mixture of regioisomers or amixture thereof.

For the sake of clarity, by the expression “a pure regioisomer or amixture of regioisomers”, or similar, it is meant the normal meaningunderstood by a person skilled in the art, i.e. that the R group ofcompound (I) may be, relative to position 1, a ortho, a meta, a parasubstituent or a mixture thereof and the R group of compound (II) maybe, relative to position 1, an ortho, a meta, a para substituent or amixture thereof. For example, the invention's composition of matter cancomprise compounds being pure regioisomers, e.g. R being a parasubstituent of the aromatic ring, relative to position 1; or a mixturesof, for example, two regioisomers comprising compounds wherein R is apara substituent of the aromatic ring, relative to position 1 andcompounds wherein R is a meta substituent of the aromatic ring, relativeto position 1. In other words, the compound of formula (I) may be offormula (I′) (i.e. R being an ortho substituent of the aromatic ring,relative to position 1), of formula (I″) (i.e. R being a metasubstituent of the aromatic ring, relative to position 1) or of formula(I′″) (i.e. R being a para substituent of the aromatic ring, relative toposition 1) or a mixture thereof and compound of formula (II) may be offormula (II′) (i.e. R being an ortho substituent of the aromatic ring,relative to position 1), of formula (II″) (i.e. R being a metasubstituent of the aromatic ring, relative to position 1), of formula(II′″) (i.e. R being a para substituent of the aromatic ring, relativeto position 1) or a mixture thereof. Each compound of formula (I′), (I″)or (I′″) represents one regioisomer of the compound of formula (I) andeach compound of formula (II′), (II″) or (II′″) represents oneregioisomer of the compound of formula (II). The compounds of formula(I′) and (II′) may also be called the ortho regioisomers. The compoundsof formula (I″) and (II″) may also be called the meta regioisomers. Andthe compounds of formula (I′″) and (II′″) may also be called the pararegioisomers.

According to any one of the above embodiments, the invention'scomposition of matter comprises at least one compound of formula (I)having a R group being a para and/or a meta substituent relative toposition 1 and at least one compound of formula (II) having a R groupbeing a para and/or a meta substituent relative to position 1.Preferably, the invention's composition of matter comprises at least onecompound of formula (I) and at least one compound of formula (II) beingthe same regioisomer, e.g. the composition of matter comprises at leastthe para regioisomer of formula (I) (compound of formula (I′″)) and atleast the para regioisomer of formula (II) (a compound of (II′″)).

According to any one of the above embodiments, the invention'scomposition of matter comprises less than 5% w/w of the metaregioisomers; i.e. of compound of formula (II″) and of compound offormula (I″). Preferably, the invention's composition of mattercomprises less than 2% w/w of the meta regioisomers; i.e. of compound offormula (II″) and of compound of formula (I″).

According to any one of the above embodiments, the invention'scomposition of matter comprises

-   -   at most 20% w/w of the compound of formula (I′);    -   at most 20% w/w of the compound of formula (II′);    -   at most 45% w/w of the compound of formula (II″);    -   at most 25% w/w of the compound of formula (I″);    -   from 25 to 99% w/w of the compound of formula (II′″);    -   from 0.5 to 49% w/w of the compound of formula (I′″);    -   wherein the percentages are expressed in a weight to weight        basis relative to the total weight of said composition of        matter.

Even more preferably, said mixture comprises

-   -   from 50 to 99% w/w of the compound of formula (II′″);    -   from 1 to 49% w/w of the compound of formula (I′″).

According to any one of the above embodiments, the invention'scomposition of matter may comprise only one regioisomer of formula (I)and only one regioisomer of formula (II) wherein the regioisomer offormula (I) is the same regioisomer of formula (II); i.e. a compositioncomprising compounds wherein the R group is an ortho substituentrelative to position 1 (composition comprising compound of formula (I′)and (II′)), or a composition comprising compounds wherein the R group isa meta substituent, relative to position 1 (composition comprisingcompound of formula (I″) and (II″)) or a composition comprisingcompounds wherein the R group is an para substituent relative toposition 1 (composition comprising compound of formula (I′″) and(II′″)). Preferably, the invention's composition of matter comprisescompounds wherein the R group is a meta or para substituent relative toposition 1. Even more preferably, the invention's composition of mattercomprises compounds wherein the R group is a para substituent relativeto position 1.

According to any one of the embodiments of the invention, said compound(I) is a compound of formula

in the form of any one of its stereoisomers or a mixture thereof, andwherein n and R¹ have the same meaning as defined above.

According to any one of the embodiments of the invention, said compound(II) is a compound of formula

wherein n and R¹ have the same meaning as defined above.

According to any one of the embodiments of the invention, said compoundof formula (I) or (II) is a C₁₂-C₁₇, or even a C₁₃-C₁₄, compound.

According to any one of the embodiments of the invention, saidinvention's composition of matter comprises compounds wherein n is 1 or2; preferably n is 1.

According to any one of the embodiments of the invention, saidinvention's composition of matter comprises compounds wherein R¹represents a hydrogen atom or a C₁₋₂ alkyl group. Preferably R¹represents a hydrogen atom or a methyl group. Most preferably, R¹represents a hydrogen atom.

According to any one of the embodiments of the invention, saidinvention's composition of matter comprises compounds wherein R²represents a hydrogen atom or a methyl group. Preferably R² represents ahydrogen atom.

According to any one of the embodiments of the invention, saidinvention's composition of matter comprises compounds wherein n is 1when R² represents a methyl group and n is 2 when R² represents hydrogenatom or a methyl group.

To the best of our knowledge, the composition of matter as herein abovereported are novel, and therefore also an object of the presentinvention.

According to any one of the above embodiments of the invention, theinvention's composition of matter comprises3-[4-(2-hydroxy-2-methylpropyl)phenyl]propanal and2-[4-(2-hydroxy-2-methylpropyl)phenyl]propanal. In particular, one maycite a composition of matter comprising3-[4-(2-hydroxy-2-methylpropyl)phenyl]propanal in an amount comprisedbetween 50% w/w and 99% w/w and2-[4-(2-hydroxy-2-methylpropyl)phenyl]propanal in an amount comprisedbetween 0.5% w/w and 49% w/w, relative to the weight of the compositionof matter. As specific examples of the invention's composition ofmatter, one may cite, as non-limiting example, a composition comprisingeven consisting of about 86% w/w of3-[4-(2-hydroxy-2-methylpropyl)phenyl]propanal and 14% w/w of2-[4-(2-hydroxy-2-methylpropyl)phenyl]propanal, relative to the weightof the composition of matter. Said composition of matter ischaracterized by having an overall olfactive character very close toLyral® (4/3-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carbaldehyde;origin International Flavors & Fragrances, USA); i.e. the invention'scomposition of matter possesses a lily of the valley, hydroxycitronellalodor note allied with a “wet” effect very typical of Lyral®. Theinvention's composition of matter may be used to impart the odor ofLyral®. In other words, the invention's composition of matter may beemployed as an olfactive substitutes for this ingredient which is highlysought by the the industry since Lyral® is now limited in use forallergenic reasons. In fact, when said composition of matter is comparedwith Lyral®, the invention's composition of matter distinguishes itselfby being more substantive and powerful (thus allowing even lower levelof dosage compared to the prior art compound) as well as having animproved radiance, while (to the contrary of many supposed substitute ofLyral®) delivering also the unique “wet” effect of Lyral®.

As mentioned above, the invention relates to the use of a composition ofmatter comprising at least one compound of formula (I) and at least onecompound of formula (II) as a perfuming ingredient. In other words, itconcerns a method to confer, enhance, improve or modify the odorproperties of a perfuming composition or of a perfumed article, whichmethod comprises adding to said composition or article an effectiveamount of at least the invention's composition of matter. By “use of acomposition of matter” it has to be understood here also the use of anycomposition containing a composition of matter and which can beadvantageously employed in the perfumery industry.

In particular, said method or use can be directed to a method to replaceLyral® in perfuming compositions. Or similarly to confer, enhance,improve or modify the floral, lily of the valley, hydroxycitronellalodor note of a perfuming composition or of a perfumed article.

Said composition of matter, which in fact can be advantageously employedas perfuming ingredient, is also an object of the present invention.

Therefore, another object of the present invention is a perfumingcomposition comprising:

-   i) as a perfuming ingredient, at least one invention's composition    of matter as defined above;-   ii) at least one ingredient selected from the group consisting of a    perfumery carrier and a perfumery base; and-   iii) optionally at least one perfumery adjuvant.

By “perfumery carrier”, it is meant a material which is practicallyneutral from a perfumery point of view, i.e. that does not significantlyalter the organoleptic properties of perfuming ingredients. Said carriermay be a liquid or a solid.

As liquid carrier one may cite, as non-limiting examples, an emulsifyingsystem, i.e. a solvent and a surfactant system, or a solvent commonlyused in perfumery. A detailed description of the nature and type ofsolvents commonly used in perfumery cannot be exhaustive. However, onecan cite as non-limiting examples solvents such as butylene or propyleneglycol, glycerol, dipropyleneglycol and its monoether,1,2,3-propanetriyl triacetate, dimethyl glutarate, dimethyl adipate1,3-diacetyloxypropan-2-yl acetate, diethyl phthalate, isopropylmyristate, benzyl benzoate, benzyl alcohol, 2-(2-ethoxyethoxy)-1-ethano,tri-ethyl citrate or mixtures thereof, which are the most commonly used.For the compositions which comprise both a perfumery carrier and aperfumery base, other suitable perfumery carriers than those previouslyspecified, can be also ethanol, water/ethanol mixtures, limonene orother terpenes, isoparaffins such as those known under the trademarkIsopar® (origin: Exxon Chemical) or glycol ethers and glycol etheresters such as those known under the trademark Dowanol® (origin: DowChemical Company), or hydrogenated castors oils such as those knownunder the trademark Cremophor® RH 40 (origin: BASF).

Solid carrier is meant to designate a material to which the perfumingcomposition or some element of the perfuming composition can bechemically or physically bound. In general such solid carriers areemployed either to stabilize the composition, or to control the rate ofevaporation of the compositions or of some ingredients. The use of solidcarrier is of current use in the art and a person skilled in the artknows how to reach the desired effect. However by way of non-limitingexample of solid carriers, one may cite absorbing gums or polymers orinorganic materials, such as porous polymers, cyclodextrines, wood basedmaterials, organic or inorganic gels, clays, gypsum talc or zeolites.

As other non-limiting examples of solid carriers, one may citeencapsulating materials. Examples of such materials may comprisewall-forming and plasticizing materials, such as mono, di- ortrisaccharides, natural or modified starches, hydrocolloids, cellulosederivatives, polyvinyl acetates, polyvinylalcohols, proteins or pectins,or yet the materials cited in reference texts such as H. Scherz,Hydrokolloide: Stabilisatoren, Dickungs-und Geliermittel inLebensmitteln, Band 2 der Schriftenreihe Lebensmittelchemie,Lebensmittelqualitat, Behr's Verlag GmbH & Co., Hamburg, 1996. Theencapsulation is a well-known process to a person skilled in the art,and may be performed, for instance, by using techniques such asspray-drying, agglomeration or yet extrusion; or consists of a coatingencapsulation, including coacervation and complex coacervationtechnique.

As non-limiting examples of solid carriers, one may cite in particularthe core-shell capsules with resins of aminoplast, polyamide, polyester,polyurea or polyurethane type or a mixture thereof (all of said resinsare well known to a person skilled in the art) using techniques likephase separation process induced by polymerization, interfacialpolymerization, coacervation or altogether (all of said techniques havebeen described in the prior art), optionally in the presence of apolymeric stabilizer or of a cationic copolymer.

Resins may be produced by the polycondensation of an aldehyde (e.g.formaldehyde, 2,2-dimethoxyethanal, glyoxal, glyoxylic acid orglycolaldehyde and mixtures thereof) with an amine such as urea,benzoguanamine, glycoluryl, melamine, methylol melamine, methylatedmethylol melamine, guanazole and the like, as well as mixtures thereof.Alternatively one may use preformed resins alkylolated polyamines suchas those commercially available under the trademark Urac® (origin: CytecTechnology Corp.), Cy Mel® (origin: Cytec Technology Corp.), Urecoll® orLuracoll® (origin: BASF).

Others resins are the ones produced by the polycondensation of a polyol,like glycerol, and a polyisocyanate, like a trimer of hexamethylenediisocyanate, a trimer of isophorone diisocyanate or xylylenediisocyanate or a Biuret of hexamethylene diisocyanate or a trimer ofxylylene diisocyanate with trimethylolpropane (known with the tradenameof Takenate®, origin: Mitsui Chemicals), among which a trimer ofxylylene diisocyanate with trimethylolpropane and a Biuret ofhexamethylene diisocyanate.

Some of the seminal literature related to the encapsulation of perfumesby polycondensation of amino resins, namely melamine based resins withaldehydes includes articles such as those published by K. Dietrich etal. in Acta Polymerica, 1989, vol. 40, pages 243, 325 and 683, as wellas 1990, vol. 41, page 91. Such articles already describe the variousparameters affecting the preparation of such core-shell microcapsulesfollowing prior art methods that are also further detailed andexemplified in the patent literature. U.S. Pat. No. 4,396,670, to theWiggins Teape Group Limited is a pertinent early example of the latter.Since then, many other authors have enriched the literature in thisfield and it would be impossible to cover all published developmentshere, but the general knowledge in encapsulation technology is verysignificant. More recent publications of pertinence, which disclosesuitable uses of such microcapsules, are represented for example by thearticle of H. Y. Lee et al. in Journal of Microencapsulation, 2002, vol.19, pages 559-569, international patent publication WO 01/41915 or yetthe article of S. Bóne et al. in Chimia, 2011, vol. 65, pages 177-181.

By “perfumery base” what is meant here is a composition comprising atleast one perfuming co-ingredient.

Said perfuming co-ingredient is not of formula (I) and (II). Moreover,by “perfuming co-ingredient” it is meant here a compound, which is usedin a perfuming preparation or a composition to impart a hedonic effect.In other words such a co-ingredient, to be considered as being aperfuming one, must be recognized by a person skilled in the art asbeing able to impart or modify in a positive or pleasant way the odor ofa composition, and not just as having an odor.

The nature and type of the perfuming co-ingredients present in the basedo not warrant a more detailed description here, which in any case wouldnot be exhaustive, the skilled person being able to select them on thebasis of his general knowledge and according to the intended use orapplication and the desired organoleptic effect. In general terms, theseperfuming co-ingredients belong to chemical classes as varied asalcohols, lactones, aldehydes, ketones, esters, ethers, acetates,nitriles, terpenoids, nitrogenous or sulphurous heterocyclic compoundsand essential oils, and said perfuming co-ingredients can be of naturalor synthetic origin or even pro-perfumes (i.e. compounds which upondegradation liberate a perfuming ingredient). Examples of pro-perfumeshave been described in the literature such as in the article publishedby A. Herrmann in Angewandte Chemie International Edition, 2007, vol.46, p. 5836-5863 or in more recent work of similar type, as well as inthe abundant patent literature in the field.

In particular one may cite perfuming co-ingredients which are commonlyused in perfume formulations, such as:

-   -   Aldehydic ingredients: decanal, dodecanal, 2-methyl-undecanal,        10-undecenal, octanal and/or nonenal;    -   Aromatic-herbal ingredients: eucalyptus oil, camphor,        eucalyptol, menthol and/or alpha-pinene;    -   Balsamic ingredients: coumarine, ethylvanillin and/or vanillin;    -   Citrus ingredients: dihydromyrcenol, citral, orange oil, linalyl        acetate, citronellyl nitrile, orange terpenes, limonene,        1-P-menthen-8-yl acetate and/or 1,4(8)-P-menthadiene;    -   Floral ingredients: Methyl dihydrojasmonate, linalool,        Citronellol, phenylethanol,        3-(4-tert-butylphenyl)-2-methylpropanal, hexylcinnamic aldehyde,        benzyl acetate, benzyl salicylate,        tetrahydro-2-isobutyl-4-methyl-4(2H)-pyranol, beta ionone,        methyl 2-(methylamino)benzoate,        (E)-3-methyl-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one,        hexyl salicylate, 3,7-dimethyl-1,6-nonadien-3-ol,        3-(4-isopropylphenyl)-2-methylpropanal, verdyl acetate,        geraniol, P-menth-1-en-8-ol, 4-(1,1-dimethylethyl)-1-cyclohexyle        acetate, 1,1-dimethyl-2-phenylethyl acetate,        4-cyclohexyl-2-methyl-2-butanol, amyl salicylate, high cis        methyl dihydrojasmonate, 3-methyl-5-phenyl-1-pentanol, verdyl        proprionate, geranyl acetate, tetrahydro linalool,        cis-7-P-menthanol, Propyl (S)-2-(1,1-dimethylpropoxy)propanoate,        2-methoxynaphthalene, 2,2,2-trichloro-1-phenylethyl acetate,        4/3-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carbaldehyde,        amylcinnamic aldehyde, 4-phenyl-2-butanone, isononyle acetate,        4-(1,1-dimethylethyl)-1-cyclohexyl acetate, verdyl isobutyrate        and/or mixture of methylionones isomers;    -   Fruity ingredients: gamma undecalactone, 4-decanolide, ethyl        2-methyl-pentanoate, hexyl acetate, ethyl 2-methylbutanoate,        gamma nonalactone, allyl heptanoate, 2-phenoxyethyl isobutyrate,        ethyl 2-methyl-1,3-dioxolane-2-acetate and/or diethyl        1,4-cyclohexane dicarboxylate;    -   Green ingredients: 2,4-Dimethyl-3-cyclohexene-1-carbaldehyde,        2-tert-butyl-1-cyclohexyl acetate, styrallyl acetate, allyl        (2-methylbutoxy)acetate, 4-methyl-3-decen-5-ol, diphenyl ether,        (Z)-3-hexen-1-ol and/or        1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one;    -   Musk ingredients: 1,4-dioxa-5,17-cycloheptadecanedione,        pentadecenolide, 3-Methyl-5-cyclopentadecen-1-one,        1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-[G]isochromene,        (1S,1′R)-2-[1-(3′,3′-dimethyl-1′-cyclohexyl)ethoxy]-2-methylpropyl        propanoate, and/or        (1S,1′R)-[1-(3′,3′-Dimethyl-1′-cyclohexyl)ethoxycarbonyl]methyl        propanoate;    -   Woody ingredients:        1-(octahydro-2,3,8,8-tetramethyl-2-naphtalenyl)-1-ethanone,        patchouli oil, terpenes fractions of patchouli oil,        (1′R,E)-2-ethyl-4-(2′,2′,3′-trimethyl-3′-cyclopenten-1′-yl)-2-buten-1-ol,        2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol,        Methyl cedryl ketone,        5-(2,2,3-trimethyl-3-cyclopentenyl)-3-methylpentan-2-ol,        1-(2,3,8,8-tetramethyl-1,2,3,4,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one        and/or isobornyl acetate;    -   Other ingredients (e.g. amber, powdery spicy or watery):        dodecahydro-3a,6,6,9a-tetramethyl-naphtho[2,1-b]furan and any of        its stereoisomers, heliotropin, anisic aldehyde, eugenol,        cinnamic aldehyde, clove oil,        3-(1,3-benzodioxol-5-yl)-2-methylpropanal and/or        3-(3-isopropyl-1-phenyl)butanal.

In particular, one may cite the following perfuming co-ingredients,having floral notes: Methyl dihydrojasmonate, linalool,3-(4-tert-butylphenyl)-2-methylpropanal, hexylcinnamic aldehyde,tetrahydro-2-isobutyl-4-methyl-4(2H)-pyranol,3,7-dimethyl-1,6-nonadien-3-ol, 3-(4-isopropylphenyl)-2-methylpropanal,4-cyclohexyl-2-methyl-2-butanol, high cis methyl dihydrojasmonate,tetrahydro linalool.

A perfumery base according to the invention may not be limited to theabove mentioned perfuming co-ingredients, and many other of theseco-ingredients are in any case listed in reference texts such as thebook by S. Arctander, Perfume and Flavor Chemicals, 1969, Montclair,N.J., USA, or its more recent versions, or in other works of a similarnature, as well as in the abundant patent literature in the field ofperfumery. It is also understood that said co-ingredients may also becompounds known to release in a controlled manner various types ofperfuming compounds.

By “perfumery adjuvant” it is meant here an ingredient capable ofimparting additional added benefit such as a color, a particular lightresistance, chemical stability, etc. A detailed description of thenature and type of adjuvant commonly used in perfuming compositioncannot be exhaustive, but it has to be mentioned that said ingredientsare well known to a person skilled in the art. One may cite as specificnon-limiting examples the following: viscosity agents (e.g. surfactants,thickeners, gelling and/or rheology modifiers), stabilizing agents (e.g.preservatives, antioxidant, heat/light and or buffers or chelatingagents, such as BHT), coloring agents (e.g. dyes and/or pigments),preservatives (e.g. antibacterial or antimicrobial or antifungi or antiirritant agents), abrasives, skin cooling agents, fixatives, insectrepellants, ointments, vitamins and mixtures thereof.

It is understood that a person skilled in the art is perfectly able todesign optimal formulations for the desired effect by admixing the abovementioned components of a perfuming composition, simply by applying thestandard knowledge of the art as well as by trial and errormethodologies.

An invention's composition consisting of at least one compound offormula (I) and at least one compound of formula (II) and at least oneperfumery carrier consist of a particular embodiment of the invention aswell as a perfuming composition comprising at least one compound offormula (I) and one compound of formula (II), at least one perfumerycarrier, at least one perfumery base, and, optionally, at least oneperfumery adjuvant.

According to a particular embodiment, the perfuming compositionsmentioned above comprise more than one compound of formula (I) and morethan one compound of formula (II) and enable the perfumer to prepareaccords or perfumes possessing the odor tonality of various compounds ofthe invention, creating thus new building block for creation purposes.

For the sake of clarity, it is also understood that any mixtureresulting directly from a chemical synthesis, e.g. a reaction mediumwithout an adequate purification, in which the invention's compositionof matter would be involved as a starting, intermediate or end-productcould not be considered as a perfuming composition according to theinvention as far as said mixture does not provide the inventivecomposition of matter in a suitable form for perfumery.

The invention's composition of matter can also be advantageously used inall the fields of modern perfumery, i.e. fine or functional perfumery,to positively impart or modify the odor of a consumer product into whichsaid invention's composition of matter is added. Consequently, anotherobject of the present invention consists of a perfumed consumer productcomprising, as a perfuming ingredient, at least one composition ofmatter comprising compound of formula (I) and compound of formula (II),as defined above.

The invention's composition of matter can be added as such or as part ofan invention's perfuming composition.

For the sake of clarity, “perfumed consumer product” is meant todesignate a consumer product which delivers at least a pleasantperfuming effect to the surface or space to which it is applied (e.g.skin, hair, textile, or home surface). In other words, a perfumedconsumer product according to the invention is a perfumed consumerproduct which comprises a functional formulation, as well as optionallyadditional benefit agents, corresponding to the desired consumer productand an olfactive effective amount of at least one invention'scomposition of matter. For the sake of clarity, said perfumed consumerproduct is a non-edible product.

The nature and type of the constituents of the perfumed consumer productdo not warrant a more detailed description here, which in any case wouldnot be exhaustive, the skilled person being able to select them on thebasis of his general knowledge and according to the nature and thedesired effect of said product.

Non-limiting examples of suitable perfumed consumer product include aperfume, such as a fine perfume, a splash or eau de parfum, a cologne ora shave or after-shave lotion; a fabric care product, such as a liquidor solid detergent, a fabric softener, a liquid or solid scent booster,a fabric refresher, an ironing water, a paper, a bleach, a carpetcleaner, a curtain-care product; a body-care product, such as a haircare product (e.g. a shampoo, a coloring preparation or a hair spray, acolor care product, a hair shaping product, a dental care product), adisinfectant, an intimate care product; a cosmetic preparation (e.g. askin cream or lotion, a vanishing cream or a deodorant or antiperspirant(e.g. a spray or roll on), a hair remover, a tanning or sun or after sunproduct, a nail product, a skin cleansing, a makeup); or a skin-careproduct (e.g. a soap, a shower or bath mousse, oil or gel, or a hygieneproduct or a foot/hand care products); an air care product, such as anair freshener or a “ready to use” powdered air freshener which can beused in the home space (rooms, refrigerators, cupboards, shoes or car)and/or in a public space (halls, hotels, malls, etc.); or a home careproduct, such as a mold remover, a furnisher care, a wipe, a dishdetergent or a hard-surface (e.g. a floor, bath, sanitary or a windows)detergent; a leather care product; a car care product, such as a polish,a waxes or a plastic cleaner.

Some of the above-mentioned perfumed consumer products may represent anaggressive medium for the invention's composition of matter, so that itmay be necessary to protect the latter from premature decomposition, forexample by encapsulation or by chemically binding it to another chemicalwhich is suitable to release the invention's composition of matter upona suitable external stimulus, such as an enzyme, light, heat or a changeof pH.

The proportions in which the composition of matter according to theinvention can be incorporated into the various aforementioned productsor perfuming compositions vary within a wide range of values. Thesevalues are dependent on the nature of the article to be perfumed and onthe desired organoleptic effect as well as on the nature of theco-ingredients in a given base when the composition of matter accordingto the invention are mixed with perfuming co-ingredients, solvents oradditives commonly used in the art.

For example, in the case of perfuming compositions, typicalconcentrations are in the order of 0.01%, or even of 1%, to 15%, or even25%, by weight, or even more, of the composition of matter based on theweight of the composition into which they are incorporated. In the caseof perfumed consumer product, typical concentrations are in the order of0.01% to 1%, or even 2%, or even more, by weight of the invention'scomposition of matter based on the weight of the consumer product intowhich they are incorporated.

Concentrations lower than these, such as in the order of 0.01% to 1%, oreven 2%, by weight, can be used when this composition of matter isincorporated into perfuming consumer products, percentage being relativeto the weight of the article.

Another object of the present invention is a process for preparing acomposition of matter comprising compound of formula (I) and compound offormula (II) as defined above. The process to prepare said compositioncomprises the step of reacting allyl alcohol or crotyl alcohol withcompound of formula

in the form of any one of its regioisomers or a mixture thereof; andwherein R¹ and R have the same meaning as above; said R being, relativeto position 1, an ortho, a meta, a para substituent of the aromatic ringor a mixture thereof; and X represents an iodide or a bromide atom or adiazo, a triflate or a tosylate group, preferably a bromide atom;under Heck coupling conditions.

For the sake of clarity, allyl alcohol is meant to designateprop-2-en-1-ol and crotyl alcohol is meant to designate but-2-en-1-ol.

For the sake of clarity, by the expression “Heck coupling conditions”,or the similar, it is meant the normal meaning understood by a personskilled in the art, i.e. the reaction is performed in a presence ofpalladium (Pd⁰) catalyst and a base. The person skilled in the art willbe able to set up the best conditions. The palladium catalyst comprisesa phosphine ligand and may be generated in situ from palladiumprecatalyst and phosphines.

The palladium catalysts or precatalysts that can be used in the presentinvention include but are not limited to Pd(dba)₂, Pd(OAc)₂,Pd[P(t-Bu₃)]₂ or Pd₂(dba)₃. Preferably, the palladium complex isselected from the group consisting of Pd(dba)₂ and Pd₂(dba)₃.

The palladium catalyst or precatalyst can be added into the reactionmedium of the invention's process in a large range of concentrations. Asnon-limiting examples, one can cite as complex concentration valuesthose ranging from about 0.1 mol % to about 10 mol %, relative to theamount of substrate. Preferably, the complex concentration will becomprised between 1 mol % to 3 mol %, relative to the amount ofsubstrate. It goes without saying that the optimum concentration ofcomplex will depend, as the person skilled in the art knows, on thenature of the latter, on the nature of the substrate, on the nature ofthe base, on the reaction temperature as well as on the desired time ofreaction.

The phosphines, that can be used in the present invention, may bemonodentate. Preferably, the phosphines that can be used in the presentinvention may be electron rich and sterically hindered; e.g. saidphosphine may comprise at least one tert-butyl or ortho-tolyl group.Even more preferably, the phosphines that can be used in the presentinvention include but are not limited to tri-tert-butylphosphine,2-(di-tert-butylphosphanyl)-1-phenyl-1H-indole,2-(di-tert-butylphosphanyl)-1-(2-methoxyphenyl)-1H-pyrrole,tri-ortho-tolylphosphine, tri(furan-2-yl)phosphane or PPh₃. Preferably,the phosphines are selected from the group consisting oftri-tert-butylphosphine, 2-(di-tert-butylphosphanyl)-1-phenyl-1H-indoleand 2-(di-tert-butylphosphanyl)-1-(2-methoxyphenyl)-1H-pyrrole. Thephosphine can be added into the reaction medium of the invention'sprocess in a large range of concentrations. As non-limiting examples,one can cite as phosphine concentration values those ranging from about0.2 mol % to about 30 mol %, relative to the amount of the of substrate.Preferably, the phosphine concentration will be comprised between 0.4mol % to 10 mol %. The optimum concentration of the phosphine willdepend, as the person skilled in the art knows, on the nature of thelatter, on the nature of the substrate, on the nature of the base, onthe reaction temperature as well as on the desired time of reaction.

The bases that can be used in the present invention include but are notlimited to potassium or sodium acetate, potassium or sodium bicarbonate,potassium or sodium carbonate, secondary or tertiary amines such astriethyl amine or N-cyclohexyl-N-methylcyclohexanamine. Preferably thebase may be N-cyclohexyl-N-methylcyclohexanamine. The amine can be addedinto the reaction medium of the invention's process in a large range ofconcentrations. As non-limiting examples, one can cite as baseconcentration values those ranging from about 1 molar equivalent toabout 3 molar equivalent, relative to the amount of the substrate.Preferably, the base concentration will be comprised between 1 molarequivalent to 1.5 molar equivalent. The optimum concentration of thebase will depend, as the person skilled in the art knows, on the natureof the latter, on the nature of the substrate, on the nature of thebase, on the reaction temperature as well as on the desired time ofreaction.

The allylic alcohol or crotyl alcohol can be added into the reactionmedium of the invention's process in a large range of concentrations. Asnon-limiting examples, one can cite as alcohol concentration valuesthose ranging from about 1 molar equivalent to about 3 molar equivalent,relative to the amount of substrate. Preferably, the alcoholconcentration will be comprised between 1 molar equivalent to 1.5 molarequivalent. It goes without saying that the optimum concentration ofcomplex will depend, as the person skilled in the art knows, on thenature of the latter, on the nature of the substrate, on the nature ofthe base, on the reaction temperature as well as on the desired time ofreaction. Preferably allyl alcohol is used.

According to any one of the above embodiments, the R group of compoundof formula (V) may be an ortho, a meta, a para substituent of thearomatic ring, relative to position 1; i.e. the compound of formula (V)may be of formula (V′), (V″), (V′″). Preferably, the compound of formula(V) is compound (V′″).

According to any one of the above embodiments, the compounds of formula(V) may be in a form of composition of matter comprising a mixture ofregioisomers; i.e. a mixture comprising a compound wherein the R groupis an ortho substituent relative to position 1 (compound of formula(V′)), a compound wherein the R group is a meta substituent, relative toposition 1 (compound of formula (V″)) and a compound wherein the R groupis an para substituent relative to position 1 (compound of formula(V′″)).

Preferably said mixture comprises

-   -   at most 40 wt % of the compound of formula (V′);    -   at most 10 wt % of the compound of formula (V″); and    -   at least 50 wt % of the compound of formula (V′″).

Even more preferably, said mixture comprises

-   -   at most 15 wt % of the compound of formula (V′);    -   at most 15 wt % of the compound of formula (V″); and    -   at least 70 wt % of the compound of formula (V′″).

Even more preferably, said mixture comprises

-   -   at most 5 wt % of the compound of formula (V′);    -   at most 5 wt % of the compound of formula (V″); and    -   at least 90 wt % of the compound of formula (V′″).

According to a preferred embodiment, the R group of compound of formula(V) is a meta and/or a para substituent of the aromatic ring, relativeto position 1; i.e. the compound of formula (V) may be of formula (V″)and/or (V′″). Preferably, the R group of compound of formula (V) is apara substituent of the aromatic ring, relative to position 1; i.e. thecompound of formula (V) is of formula (V′″).

According to any one of the above embodiments, the compound of formula(V) can be prepared according to methods reported in the literature orstandard methods known in the art; for example, by the functionalizationof a benzene derivative of formula (VI)

in the form of any one of its regioisomers or a mixture thereof; andwherein R¹ and R have the same meaning as above.

According to a particular embodiment of the invention, the compound offormula (V) can be prepared by the bromation of2-methyl-1-phenylpropan-2-ol or 2-methyl-4-phenylbutan-2-ol which arecommercially available. Said method provides different regioisomerswhich could be purified or use as a mixture.

According to another particular embodiment of the invention, thecompound of formula (V) can be prepared by the addition of a MethylGrignard on an alkyl (bromophenyl)acetate.

According to a particular embodiment, the process to prepare theinvention's composition of matter comprises the step of reacting methylor ethyl acrylate instead of allylic alcohol with compound of formula(V) under Heck coupling conditions. In order to obtain the invention'scomposition of matter, the compounds obtained via said Heck couplinghave to be reduced under conditions known by the person skilled in theart.

According to any one of the above embodiments, the compound of formula(V) is a compound of formula

wherein R¹ has the same meaning as defined above.

The Heck coupling reaction can be carried out in the presence of asolvent. Any solvent current in such reaction type can be used for thepurposes of the invention. Non-limiting examples include dioxane,dimethyl sulfoxide, acetonitrile, C₆₋₁₂ aromatic solvents such astoluene, 1,3-diisopropylbenzene, cumene or pseudocumene, amide suchN,N-dimethylformamide or N-methylformamide, or mixtures thereof. Thechoice of the solvent is a function of the nature of the substrateand/or catalyst and the person skilled in the art is well able to selectthe solvent most suitable in each case to optimize the reaction.

The Heck coupling step can be carried out at a temperature in the rangecomprised between 20° C. and 120° C., more preferably in the range ofbetween 80° C. and 110° C., or even between 90° C. and 100° C. Ofcourse, a person skilled in the art is also able to select the preferredtemperature according to the melting and boiling point of the startingand final products as well as the desired time of reaction orconversion.

It is understood that the composition of matter, may comprise variousregioisomers, such as the ortho, para or meta products depending on thepurity of the staring materials.

EXAMPLES

The invention will now be described in further detail by way of thefollowing examples, wherein the abbreviations have the usual meaning inthe art, the temperatures are indicated in degrees centigrade (° C.);the NMR spectral data were recorded in CDCl₃ (if not stated otherwise)with a 400 or 500 MHz machine for ¹H and ¹³C, the chemical shifts 8 areindicated in ppm with respect to TMS as standard, the coupling constantsJ are expressed in Hz.

Example 1 Preparation of invention's composition comprising2-(4-(2-hydroxy-2-methylpropyl)phenyl)propanal (compound of formula (I))and 3-(4-(2-Hydroxy-2-methylpropyl)phenyl)propanal (compound of formula(II)) a) Preparation of 1-(4-Bromophenyl)-2-methylpropan-2-ol

A 200 ml round bottomed flask were charged methylmagnesium bromide (19g, 3M in methyltetrahydrofuran, 57 mmol) and 2-methyltetrahydrofuran (25g). This solution was stirred at 0° C. A solution of ethyl2-(4-bromophenyl)acetate (5 g, 20.6 mmol) in 2-methyltetrahydrofuran (15g) was added over a period of 30 minutes. The reaction mixture was thenstirred further for 3 hours. The reaction mixture was quenched withacetic acid (30 g, 20% aqueous solution) and phases were separated. Theorganic phase was washed with water, 5% Na₂CO₃ solution, water andevaporated down to yield crude 1-(4-bromophenyl)-2-methylpropan-2-ol(4.4 g) which was purified by distillation (3.85 g, 82% yield).

¹H NMR (500 MHz, CDCl₃): δ=1.20 (s, 6H), 1.45 (br, 1H), 2.70 (s, 2H),7.10-7.06 (m, 2H), 7.44-7.40 (m, 2H) ppm.

¹³C NMR (125 MHz, CDCl₃): δ=136.8 (s), 132.1 (d), 131.2 (d), 120.5 (s),70.6 (s), 49.1 (t), 29.2 (q) ppm.

b) Preparation of a 1-(4-Bromophenyl)-2-methylpropan-2-ol and1-(2-Bromophenyl)-2-methylpropan-2-ol

To a solution of 2-methyl-1-phenylpropan-2-ol (91.5 g, 609 mmol, 1equiv.) and iron (III) chloride (9.88 g, 60.9 mmol, 0.1 equiv.) inacetonitrile (305 mL) was added 1,3-dibromo-5,5-dimethylhydantoin (96 g,335 mmol, 0.55 equiv.) portionwise. After stirring at r.t. for 3 days,the reaction was quenched with water. It was extracted twice with ether,the combined organic extracts were washed with a 10% sodium thiosulfatesolution, dried over sodium sulfate and the solvents were evaporated.The residue was purified by bulb-to-bulb distillation (0.07 mbar, 75°C.) and distillation on a Fischer column to afford pure1-(4-bromophenyl)-2-methylpropan-2-ol (57.1 g, 41% yield) and pure1-(2-bromophenyl)-2-methylpropan-2-ol (34.2 g, 25% yield).

1-(4-bromophenyl)-2-methylpropan-2-ol

¹H NMR (500 MHz, CDCl₃): δ=1.21 (s, 6H), 2.71 (s, 2H), 7.09 (d, J=8.3Hz, 2H), 7.43 (d, J=8.3 Hz, 2H).

¹³C NMR (125 MHz, CDCl₃): δ=136.8 (s), 132.2 (d, 2C), 131.2 (d, 2C),120.5 (s), 70.7 (s), 49.1 (t), 29.2 (q, 2C).

1-(2-bromophenyl)-2-methylpropan-2-ol

¹H NMR (500 MHz, CDCl₃): δ=1.28 (s, 6H), 3.01 (s, 2H), 7.08 (m, 1H),7.25 (m, 1H), 7.35 (dd, J=7.7, 1.7 Hz, 1H), 7.57 (dd, J=8.0, 1.2 Hz,1H).

13C NMR (125 MHz, CDCl₃): δ=137.7 (s), 133.1 (d), 132.3 (d), 128.1 (d),127.1 (d), 126.0 (s), 71.8 (s), 48.0 (t), 29.5 (q, 2C).

c) Preparation of a composition comprising2-(4-(2-hydroxy-2-methylpropyl)phenyl)propanal and3-(4-(2-hydroxy-2-methylpropyl)phenyl)propanal

In a 100 ml round bottomed flask were charged under an argon atmosphere1-(4-Bromophenyl)-2-methylpropan-2-ol (5 g, 21.7 mmol), N,N-dimethylformamide (10 g), N-cyclohexyl-N-methylcyclohexanamine (4.8 g, 23.8mmol) and allyl alcohol (1.38 g, 23.8 mmol); this solution was degassedfor one hour. 2-(di-tert-butylphosphino)-1-phenyl-1H-indole (0.093 g,0.26 mmol) and bis(dibenzylideneacetone)palladium (0) (0.052 g, 0.09mmol) were added and the reaction mixture was heated at 100° C. for 1hour, then cooled to room temperature. The mixture was diluted withtoluene and washed with water, 10% aqueous HCl, 5% NaHCO₃ solution andwater. Organic phase was concentrated to furnish crude (3.9 g) which waspurified by distillation (3.05 g, 68% yield, containing 15% of2-(4-(2-hydroxy-2-methylpropyl)phenyl)propanal and 85% of3-(4-(2-hydroxy-2-methylpropyl)phenyl)propanal).

3-(4-(2-hydroxy-2-methylpropyl)phenyl)propanal

¹H NMR (500 MHz, CDCl₃): δ=1.21 (s, 6H), 1.64-1.56 (br, 1H), 2.72 (s,2H), 2.79-2.74 (m, 1H), 2.93 (t, 2H), 7.16-7.1 (m, 4H), 9.8 (t, 1H) ppm.

¹³C NMR (125 MHz, CDCl₃): δ=201.7 (s), 138.4 (s), 135.8 (s), 130.7 (d),128.1 (d), 70.7 (s), 49.3 (t), 45.2 (t), 29.2 (q), 27.7 (t) ppm.

2-(4-(2-hydroxy-2-methylpropyl)phenyl)propanal

¹H NMR (500 MHz, CDCl₃): δ=1.23 (s, 6H), 1.44 (d, J=7.0 Hz, 3H), 2.76(s, 2H), 3.62 (dd, J=7.0, 1.4 Hz, 1H), 7.15 (d, J=8.1 Hz, 2H), 7.24 (d,J=8.1 Hz, 2H), 9.67 (d, J=1.4 Hz, 1H).

¹³C NMR (125 MHz, CDCl₃): δ=201.1 (d), 137.2 (s), 135.8 (s), 131.2 (d,2C), 128.1 (d, 2C), 70.8 (s), 52.6 (d), 49.3 (t), 29.2 (q, 2C), 14.6(q).

Example 2 Preparation of invention's composition comprising2-(4-(2-hydroxy-2-methylpropyl)phenyl)propanal (compound of formula (I))and 3-(4-(2-hydroxy-2-methylpropyl)phenyl)propanal (compound of formula(II)) using different phosphines

The same procedure reported in example 1 c) has been reproduced byreplacing 2-(di-tert-butylphosphino)-1-phenyl-1H-indole by the sameamount in mmol of phophines reported in Table 1.

TABLE 1 Phosphine used in Heck reaction conditions % Conv. % Conv. %Conv. l/b Phosphine 1 h 2.5 h 6 h ratio 2-(di-tert-butylphosphino)- 99.199.6 100 85/15 1-phenyl-1H-indole P(tBu)₃HBF₄ 95 98.4 100 85/15P(o-Tolyl)₃ 90 90 90 85/15 P(Phenyl)₃ 10 24 26 82/18

Example 3 Preparation of invention's composition comprising2-(3-(2-hydroxy-2-methylpropyl)phenyl)butanal (compound of formula (I))and 3-(3-(2-hydroxy-2-methylpropyl)phenyl)butanal (compound of formula(II)) a) Preparation of 1-(3-bromophenyl)-2-methylpropan-2-ol

To a solution of 1,3-dibromobenzene (27.1 g, 115 mmol, 1 equiv.) in THF(383 mL) at −78° C. was added n-BuLi (1.6 M, 79 mL, 127 mmol, 1.1equiv.) dropwise. After stirring at −78° C. for 1.5 hour, thetemperature was allowed to reach −50° C. and isobutylene oxide (12.3 mL,138 mmol, 1.2 equiv.) was added dropwise. After stirring at −50° C. for30 min, boron trifluoride etherate (19.0 mL, 150 mmol, 1.3 equiv.) wasadded dropwise. After stirring at −50° C. for 1.5 hour, the reaction wasquenched with a 10% w/w solution of Na/K tartrates and the mixture wasallowed to reach room temperature overnight. It was extracted threetimes with ether, the combined organic extracts were dried over sodiumsulfate and the solvent was evaporated. The residue was purified bybulb-to-bulb distillation (125-130° C., 0.24-0.30 mbar) to afford1-(3-bromophenyl)-2-methylpropan-2-ol as an oil (16.3 g, 91% purity, 57%yield).

¹H NMR (500 MHz, CDCl₃): δ=1.23 (s, 6H), 2.73 (s, 2H), 7.13-7.19 (m,2H), 7.37-7.39 (m, 2H).

¹³C NMR (125 MHz, CDCl₃): δ=140.2 (s), 133.4 (d), 129.7 (d), 129.6 (d),129.1 (d), 122.2 (s), 70.8 (s), 49.3 (t), 29.2 (q, 2C).

b) Preparation of a composition comprising2-(3-(2-hydroxy-2-methylpropyl)phenyl)butanal (compound of formula (I))and 3-(3-(2-hydroxy-2-methylpropyl)phenyl)butanal (compound of formula(II))

A solution of 1-(3-bromophenyl)-2-methylpropan-2-ol (5.00 g, 18.8 mmol,1 equiv.) and N-cyclohexyl-N-methylaminecyclohexanamine (4.73 mL, 20.6mmol, 1.1 equiv.) in DMF (37.5 mL) was degassed and stirred under anargon atmosphere for 20 min. Crotyl alcohol (1.76 mL, 20.6 mmol, 1.1equiv.) and bis(dibenzylideneacetone)palladium(0) (108 mg, 0.19 mmol,0.01 equiv.) were added, followed by2-(tert-butylphosphino)-1-phenyl-1H-indole (190 mg, 0.56 mmol, 0.03equiv.) and the reaction was heated to 100° C. for 45 min. After coolingdown to r.t., it was diluted with ether and washed three times withwater. The organic layer was dried over sodium sulfate and the solventwas evaporated. The residue (GC ratio of linear/branched products:2.5:1) was purified by flash column chromatography on silica gel(Heptane/AcOEt 7:3) and bulb-to-bulb distillation (130-140° C., 0.15mbar) to afford the desired3-(3-(2-hydroxy-2-methylpropyl)phenyl)butanal (1.62 g, 39% yield) and2-(3-(2-hydroxy-2-methylpropyl)phenyl)butanal (586 mg, 14%).

3-(3-(2-hydroxy-2-methylpropyl)phenyl)butanal

¹H NMR (500 MHz, CDCl₃): δ=1.22 (s, 6H), 1.32 (d, J=7.0 Hz, 3H),2.63-2.78 (m, 2H), 2.75 (s, 2H), 3.35 (sext, J=7.1 Hz, 1H), 7.06-7.12(m, 3H), 7.25 (m, 1H), 9.70 (t, J=2.0 Hz, 1H).

¹³C NMR (125 MHz, CDCl₃): δ=201.8 (d), 145.3 (s), 138.2 (s), 129.1 (d),128.7 (d), 128.5 (d), 124.8 (d), 70.7 (s), 51.8 (t), 49.7 (t), 34.2 (d),29.2 (q, 2C), 22.2 (q).

2-(3-(2-hydroxy-2-methylpropyl)phenyl)butanal

¹H NMR (500 MHz, CDCl₃): δ=0.90 (t, J=7.4 Hz, 3H), 1.22 (s, 6H), 1.76(m, 1H), 2.11 (m, 1H), 2.77 (s, 2H), 3.40 (m, 1H), 7.04 (s, 1H), 7.08(d, J=7.6 Hz, 1H), 7.16 (d, J=7.6 Hz, 1H), 7.31 (t, J=7.6 Hz, 1H), 9.67(d, J=2.0 Hz, 1H).

¹³C NMR (125 MHz, CDCl₃): δ=201.0 (d), 138.7 (s), 136.2 (s), 131.0 (d),129.6 (d), 128.8 (d), 126.9 (d), 70.7 (s), 60.7 (d), 49.6 (t), 29.2 (q,2C), 23.0 (t), 11.7 (q).

What is claimed is:
 1. A composition of matter comprising: a) at leastone compound of formula

in the form of any one of its isomers or a mixture thereof; wherein R¹represents a hydrogen atom or a C₁₋₂ alkyl group; R² represents ahydrogen atom or a methyl group; and R represents a group of formula[CH₂]_(n)C(Me)₂OH, wherein n is 1 or 2; said R being, relative toposition 1, an ortho, a meta, a para substituent of the aromatic ring ora mixture thereof; and b) at least one compound of formula

in the form of any one of its isomers or a mixture thereof; wherein R¹,R² and R have the same meaning as defined in formula (I); said R being,relative to position 1, an ortho, a meta, a para substituent of thearomatic ring or a mixture thereof.
 2. The composition according toclaim 1; wherein the compound of formula (I) is of formula

in the form of any one of its stereoisomers or a mixture thereof, andwherein n and R¹ have the same meaning as defined in claim
 1. 3. Thecomposition according to claim 1; wherein the compound of formula (II)is of formula

wherein n and R¹ have the same meaning as defined in claim
 1. 4. Thecomposition according to claim 1, wherein R¹ is a hydrogen atom.
 5. Thecomposition according to claim 1, wherein n is
 1. 6. The compositionaccording to claim 1, wherein the composition comprises2-(4-(2-hydroxy-2-methylpropyl)phenyl)propanal and3-(4-(2-hydroxy-2-methylpropyl)phenyl)propanal.
 7. The compositionaccording to claim 6; wherein the composition comprises3-[4-(2-hydroxy-2-methylpropyl)phenyl]propanal in an amount comprisedbetween 50% w/w and 99% w/w and2-[4-(2-hydroxy-2-methylpropyl)phenyl]propanal in an amount comprisedbetween 0.5% w/w and 49% w/w, relative to the weight of the compositionof matter.
 8. A perfuming composition comprising i) at least acomposition of matter as defined in claim 1; ii) at least one ingredientselected from the group consisting of a perfumery carrier and aperfumery base; and iii) optionally at least one perfumery adjuvant. 9.A perfuming consumer product comprising at least a composition of matteras defined in claim
 1. 10. The perfuming consumer product according toclaim 9, wherein the perfumery consumer product is a perfume, a fabriccare product, a body-care product, a cosmetic preparation, a skin-careproduct, an air care product or a home care product.
 11. A perfumingconsumer product according to claim 10, wherein the perfumery consumerproduct is a fine perfume, a splash or eau de perfume, a cologne, anshave or after-shave lotion, a liquid or solid detergent, a fabricsoftener, a fabric refresher, an ironing water, a paper, a bleach, acarpet cleaners, curtain-care products a shampoo, a coloringpreparation, a color care product, a hair shaping product, a dental careproduct, a disinfectant, an intimate care product, a hair spray, avanishing cream, a deodorant or antiperspirant, hair remover, tanning orsun product, nail products, skin cleansing, a makeup, a perfumed soap,shower or bath mousse, oil or gel, or a foot/hand care products, ahygiene product, an air freshener, a “ready to use” powdered airfreshener, a mold remover, furnisher care, wipe, a dish detergent orhard-surface detergent, a leather care product, a car care product. 12.A process to prepare the composition of matter as defined in claim 1comprising the step of reacting allyl alcohol or crotyl alcohol withcompound of formula

wherein R¹ and R have the same meaning in any one of claims 1 to 7; saidR being, relative to position 1, an ortho, a meta, a para substituent ofthe aromatic ring or a mixture thereof; and X represents an iodide or abromide atom or a diazo, a triflate or a tosylate group; under Heckcoupling conditions.
 13. The process according to claim 12, whereinprocess is performed in a presence of palladium (Pd⁰) catalyst and abase.
 14. A method to confer, enhance, improve or modify the odorproperties of a perfuming composition or of a perfumed article, whichmethod comprises adding to said composition or article an effectiveamount of at least a composition of matter as defined in claim
 1. 15. Aperfuming consumer product comprising a perfuming composition comprisingi) at least a composition of matter as defined in claim 1; ii) at leastone ingredient selected from the group consisting of a perfumery carrierand a perfumery base; and iii) optionally at least one perfumeryadjuvant.
 16. The perfuming consumer product according to claim 9,wherein the perfumery consumer product is a perfume, a fabric careproduct, a body-care product, a cosmetic preparation, a skin-careproduct, an air care product or a home care product.
 17. The perfumingconsumer product according to claim 16, wherein the perfumery consumerproduct is a fine perfume, a splash or eau de perfume, a cologne, anshave or after-shave lotion, a liquid or solid detergent, a fabricsoftener, a fabric refresher, an ironing water, a paper, a bleach, acarpet cleaners, curtain-care products a shampoo, a coloringpreparation, a color care product, a hair shaping product, a dental careproduct, a disinfectant, an intimate care product, a hair spray, avanishing cream, a deodorant or antiperspirant, hair remover, tanning orsun product, nail products, skin cleansing, a makeup, a perfumed soap,shower or bath mousse, oil or gel, or a foot/hand care products, ahygiene product, an air freshener, a “ready to use” powdered airfreshener, a mold remover, furnisher care, wipe, a dish detergent orhard-surface detergent, a leather care product, a car care product.